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United States Patent 0 BENZYL ETHERS 0F ALKYLPHENUXYPOLY- ETHOXYETHANOLWarren D. Niederhauser, Hunting-don Valley, and Edwin J. Smialkowski,Philadelphia, Pa., assignors to Robin & Haas Company, Philadelphia, Pa,a corporation of Delaware No Drawing. Application March 22, 1954 SerialNo. 417,939

13 Claims. (Cl. 260-613) This invention relates to low-foaming non-ionicsurface-active compositions. It also relates to a process by which thesecompositions are prepared.

The compounds of the present invention are represented by the formula nwCH2OH2),.O ontotm wherein R is an alkyl group of eight to fifteen carbonatoms and n is an integer from twelve to forty. The process by whichthese compounds are prepared comprises reacting a compound of theformula in which R is an alkyl group of eight to fifteen carbon atomsand n is an integer from twelve to forty, with benzyl chloride orbromidein the presence of a strongly basic inorganic neutralizing agent.The use of benzyl chloride is somewhat preferable to the use of benzylnwomornnon wherein R is an alkyl group of eight to fifteen carbon atomsand n is an integer from twelve to forty, are.

known and available, and usually exhibit surface activity in varyingdegrees of practical utility. A unit or two of propylene oxide may be"substituted for a similar amount of ethylene oxide withoutsubstantially altering the identifying characteristics of the compound.Propylene oxide and ethylene oxide are equivalent to this extent. Theformation of a benzyl ether from the abovetype compound results in aproduct having low-foam detergent properties superior to those of theparent compound.

Although the compounds prepared by the use of benzyl chloride or bromideare considered of the greatest practical importance,satisfactorily-useful compounds may be prepared from substituted benzylchloride or bromide. The substituents on the benzene ring should berelatively inert to the reaction components of the present invention andmay include the chloro, bromo, nitro, or lower alkyl groups. Compoundsthat have been found to be suitable include a number having alkylgroups, chlorine or bromine atoms, nitro groups, or combinationsthereof,

More- 2,856,434 Patented Oct. 14, 1958 attached to a benzene ring as,for example, methylbenzyl chloride, dimethylbenzyl chloride,trimethylbenzyl chloride, ethylbenzyl chloride, ethylmethylbenzylchloride, chlorobenzyl chloride, bromobenzyl chloride,chloromethylbenzyl chloride, nitrobenzyl chloride, and the like. Thecorresponding bromides are likewise suitable.

In the formula R 0 ornom)..on

R has been defined as an alkyl group of eight to fifteen carbon atoms.Actually, there may be more than one alkyl substituent on the benzenering. It is only important that the total number of carbon atoms in allof the alkyl substituents range between eight and fifteen. Suitable forthis use are the octyl, nonyl, decyl, dodecyl or pentadecyl groups assingle substituents for R. Two

groups may also be substituted for R, as, for example, an octyl and anamyl, a nonyl and an amyl, a decyl and a propyl, a decyl and an amyl, ora dodecyl and a propyl. Even three groups may be substituted for R, as,for example, three amyl substituents. The positions or the alkyl groupson the benzene rings are not indicated because they are not critical. t

The number of ethoxy units employed may be varied,

as desired, within the range of twelve to forty. The

presence of twelve ethoxy units gives the compound a hydrophilic traitsufficient to assure water solubility when the alkyl substituent is anoctyl group. The presence of additional ethoxy units tends to increasethe water solubility of the present compounds which is particularlydesirable as the alkyl substituent approaches the limit of fifteencarbon atoms. Compounds of the subject type exhibit the property ofinverse solubility. That is, for

instance, as the temperature of an aqueous 1% solution is increased apoint is reached where a turbidity appears. I

This is called the cloud point. As the number of ethoxy units isincreased the cloud point gradually rises. instance, the cloud point ofthe octyl compound having the lowest number of ethoxy units contemplatedwithin this invention, that is, twelve, is less than 2 C. With fifteenethoxy units the cloud point has risen to 15 C.; with sixteen ethoxyunits the cloud point is 18 C.; with seventeen ethoxy units the cloudpoint is 23 C.;

with twenty ethoxy units the cloud point has increased. -to 39 C.; andwith the greatest number of ethoxy units,

forty, the cloud point has reached 52 C.

Of course, in some respects, there is a gradation of chemical andphysical properties in considering the gamut of ethoxy units in thecompounds. Generally, for instance, the lower members are excellentdetergents, while the higher members are, in addition, good emulsifiers.While all of the compounds, regardless of the number of ethoxy units,are excellent detergents with good foam 1 characteristics, the lowermembers give the best foam results.

In the formation of the alkylphenoxypolyethoxyethan- 01s in the range oftwelve to forty ethoxy units, there is sometimes obtained a mixture ofcompounds having different numbers of ethoxy units. This is known and isno deterrent to the present reaction since satisfactory and usefulcompounds are formed from the mixture of compounds in the same way asthe individual compounds.

the suitable agents that may be used are the alkali metals,

such as sodium and potassiums, sodium hydroxide, potassium hydroxide,sodium methoxide, potassium methoxide,

For I The choice of a specificpotassium ethoxide; sodium butoxide,sodium carbonate,lithiumhydroxide;-the'alkaliearth--metal-hydroxides;-such as bariumhydroxide, calcium hydroxide and strontium hydroxide, and the like. Thealkali agent should be present in an amountsomewhat; greaterthanthemolar amount of the alkylphenoxypolyethoxyethauol. "This is desirable toassure the complete --'neutralization of the hydrochloric torhydrobromic acid formed in thereaction. The exeess agent causes nointerference-with the desired result and may-easily be removed at=a-eonvenient later stage.

The reaction will satisfactorily occur in the range of temperatures fromabout 50 "to 200 C. The preferred range is about 100 to 150, C. "Thetemperature. of the reaction is t not extremely -critical I andtemperatures may be-usrdother-than those mentioned. Howeverfithe bestresults are obtained -using-thetemperature ranges set forth above.

*The *reactionqis essentially i-cornpleted at the end .of about-"onehour althougha somewha't longer reaction time is usually provided -to*assure maximumresults. *The yieldsconsistently-average 93--to -97'% ofthe benzylether product-based on-=the weight ofthe alcohol used.

1f desired; the-reactio11 *may -be conducted in the; presenceofa'volatileyinert'organic solvent. Suitableffor1'this use-arebenzene,-xylene, toluen e -and the; like. The use of sueh solve'nts isamatter of'choice' because thereaction proceeds satisfactorily without asolvent.

:At the conclusion =of the reaction 'the excess unused reactantsareremovedfrom 'the productby'standardprocedures. The-reaction mixtureis--washed with-water land -the. wash'water discarded. If*desired, aninert volatile-hydrocarbon solvent such asf-benzene. toluene, or thelike, may be used-to' aidintheseparation of the water layer from theproduct layer. 'This is-not usually necessary and, if--not-'necessary,-would -not beused because su'cha step would add the -problem of removalof the hydrocarbon solvent-from the'product' layer. Unreactedbenzyl-chloride or bromide and-formed benzyl alcohol are-preferablyremoved by vacuum steam distillation. The-product-is finally dried,preferably under-vacuum at any convenient temperature, and filtered.

The-method offorma'tion of'the products of this inven tion is set'forthin the following illustrative examples. Parts by wei'ght are used'throughout.

.lExample l glntovi'a. fiaslercquipped -with a stirrer aud-azthcrmometer 82tpartssof 0.10 H210 B913 H layer wasisteamastrippedto'remove toluene, :benzylzchloride, and benzylyalcohol. The-:productwasdried,'by heatingto;100-C.-at5-20 pressure-and filtered. The yield fthebenzyl ether .of

immtoetumt0it was' 860 pa-rts which= represents 95%aof-thattheoretically possible. The color: of '-the-;.product= wasequiv'alent -to ahoute4 .on'ithe Gardner-color: scale (Standards *of1-933). Therproduct-ahadua. cloudapoint of. 1 5 C.

"analogous manner.

Example 2 There was added to 747 parts of in a flask 50 parts of sodiumhydroxide. The temperature was-raised to to-.80 C-to-acceleratedhendissolution-'ofzsodium hydroxide. To the rtiixturefwasadded llSzpartsof benzyl chloride "over-a peritaiddfBO-minutes and thetemperature of the system was increasedtolIO to C. The mixturewasstirred for. three; hours at which time 200 parts of "water was'addedand the temperature raised to the boiling point of thecontents of theflask. The mixture'wasallowed to-settle'and form layers. The aqueouslower layer was discarded and the product upper layer :wassteam strippedto remove benzyl alcohol and benzyl chloride. The product was dried; byheating to 100 C. at 20 mm. pressure; and "filtered. 'Theproduct hadgaGardner'teolor value of about 3 and a :cloud point of about 2 C. Theyield was 811 parts (97% 'o'f theoretical) Benzyl bromide "functions ina manner similar to benzyl chloride in this reaction. Metallic sodium orpotassium or calcium hydroxide-maybe used as the alkali agent toproducesimilan results.

The corresponding dodecyl- -and pentadecyl"alcohols=react to formsimilar products'in a-waysimilar-tmthe octyl alcohol.

---Example.3

rIQQSImat-ts of 701-par-ts of potassium*-hydrox'ide'was ad'ded. 0verjaperiod of about --3 0-minutes '180-parts of benzyl chloride wasadded-and the temperature of the-system was, raised to=-l25ato "C.The'mixturewasstirredfor about three hoursandthen-ZOOparts ofwater wereadded. The temperature of-"the system was raised' to" the-boiling pointand then**th e mixture-was allowed tosettle. and formilayers. 'T-Theaqueous lowerla-yer was discarded and 'the product upper layer was-steam stripped to removewoiatile components. '1' he product was-drie'd""by .hcatiugdto 100-'- to 05 ---'C. "at 22 mm. pressureanddilteretl.

. product hada Gardner colorwalue'of -"about 4 and -a"cloud point of 23C. The yield of the benzylether was 1002 parts (96% of theoretical).

The corresponding nonyl and decyl alcohols react similarly to the octylalcohol.

Example-.4

' To. a .mixtuteQf;1086 parts of discarded. "The upper layer-was steamstrippedyand'then drie'dand-filtered. Ayield of "l'096 parts j(93'%o'fftheoretical) --was obtained. The color 'of'the pro'ductwas about'5on the Gardner scale. It'had a cloudpoint'o'f 39C.

The corresponding Pdecylamyl --alcohol-- works satisfactorily inthisexample.

Example A 60-part portion of sodium methoxide was added to 1966 parts ofI To this mixture, 175 parts of benzyl chloride was added over a periodof 28 to 30 minutes. The temperature of the system was adjusted to 120to 135 C. for a period of three hours. Water was added and a separationinto layers efiected. The water layer was discarded and the productlayer was steam stripped to remove volatile components. The product wasdried by he'atingand then filtered. A yield of 1961 parts (95%oftheoreticallwas obtained. The benzyl ether product had a color of 4 to5 on the Gardner color scale and a cloud point of 52 C.

Sodium or potassium hydroxide produces results similar to those producedby sodium methoxide.

Example 6 There were added to 1540 parts of 100 parts of potassiumethoxide and 200 parts of benzyl bromide. The temperature of the systemwas raised to 135 to 150 C. and maintained at that level for about twoand one-half hours. Water was added to the mixture and the temperaturewas increased to the boiling point. The mixture was allowed to settleand separate into layers. The aqueous lower layer was discarded and theproduct upper layer was steam stripped to remove benzyl alcohol andbenzyl bromide. The product was dried and filtered. The yield was 1549parts (95% of theoretical).

Benzyl chloride produces the same result as benzyl bromide. Sodiummethoxide and sodium ethoxide per form in the same manner as potassiumethoxide.

Example 7 There was added to a mixture of 910 parts of osnnt emanationand 50 parts of sodium hydroxide 180 parts of benzyl chloride. Thebenzyl chloride was added at a rate of about 6 parts per minute duringwhich time the tempera ture of the system was raised to 135 to 150 C.The temperature was maintained at this level for about two hours andthen water was added to the system. The mixture formed layers and thewater layer was removed and discarded. The product layer was steamstripped, dried, and filtered. The benzyl ether product was obtained inthe amount of 952 parts (95% of theoretical). The Gardner color value ofthe product was about 5 and the cloud point was 18 C.

Detergency and foam characteristics were determined on the productsobtained from the above examples. All were excellent detergents whentested under dishwashing and laundering conditions. For instance, theoctyl product containing 20 ethoxy units in the amount of 10 parts, inconjunction with 90 parts of an alkaline builder which was made up of60% sodium tripolyphosphate, 20% sodium silicate, and 20% sodiumsulfate, gave a 95% detergency rating in a standard mechanicaldishwashing test which is markedly superior to known commercialdetergents.

The foam characteristics of these compounds at 70 C. were determinedunder simulated mechanical dishwashing conditions. All were excellent.The following shows the foam results on the octyl compounds:

Foam heights in cm; Compound with 12 ethoxy units 0.0 Compound with 15ethoxy units 0.0 Compound with 16 ethoxy units 0.0

Compound with 17 ethoxy units 0.0

These results indicated foam characteristics superior to those of knowncommercial compounds of the corresponding polyethoxy alcohol type whichunder identical conditions gave foam heights of 9.0 to 11.8 cm. The

wherein R is an alkyl group of eight to fifteen carbon atoms and n is aninteger from twelve to forty.

2. As a composition of matter the compound having the formula C7Hi1 (OCHgCHDuO CHgCuHs 3. As a composition of matter the compound having theformula 0.1119 (0 CHzCHzhaO CHzCaHIi 4. As a composition of matter thecompound having the formula ClHn (OCH:CH5)z0O CHmCsHs 5. As acomposition of matter the compound having the formula 00H" (OCHgCHDWOCHrC6 5 6. As a composition of matter the compound having the formula 7.A process for the preparation of compounds having the formula wherein Ris an alkyl group of eight to fifteen carbon atoms and n is an integerfrom twelve to forty, comprising reacting a benzyl compound from theclass consisting of benzyl bromide and benzyl chloride with an alcoholhaving the formula R (OOH:CHz)..OH

wherein R and n have the same significance as above, in the presence ofa strongly basic inorganic neutralizing agent at a temperature of about50 to 200 C., and then separating the product. i

8. A process as defined in claim 7 wherein R is an octyl group and n isequal to 12.

9. A process as defined in claim 7 wherein R is a nonyl group and n isequal to 15.

10. A process as defined in claim 7 wherein R is an octyl group and n isequal to 20.

11. A process as defined in claim 7 wherein R is a nonyl group and n isequal to 30.

12. A process as defined in claim 7 wherein R is an octyl group and n isequal to 40.

13. A process for the preparation of compounds having the formulawherein R is an alkyl group of eight to fifteen carbon atoms and n is aninteger; from: twelve to forty, comprising reacting a benzyl compound.from. the class consisting of bromide and chloride with an alcoholhaving the formula,

womcmnon wherein R and n have the same significance as" above,

in the presence of'anexcessof zr-,strong-1y-basic inorganic"neutralizing agent at a-temperatureof'a-bout 50 to 200 C., then Washingthe reaction mixture with Water, removing the volatile components bydistillation, drying by heating up to 100' C; at" about 20 mm. pressure,and obtaining the product as the residue.

References Cited. in thefile of this patent UNITED STATES PATENTS2,178,831

OTHER REFERENCES Schwartz et al;; Surface Active Agents 1949 pp. 18,,

LUncist'ed et aL; Journal Amer. Oil Chemists Society, vol. 285 (1951),p. 295.

Main

UNITED STATES PATENT OFFICE Certificate of Correction Patent No.2,856,434 October 14, 1958 Warren D. Niederhauser et a1.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction and that the saidLetters Patent should read as corrected below.

Column 4, lines 34 to 36, Example 3, the formula should appear as shownbelow instead of as in the patenta nwCHaCH2h1OH column 6, lines 21 to23, claim 2, the formula should appear as shown below instead of as inthe patent CsH1 (0CEnCHg)uOCHQOQH5 lines 41 to 43, claim 6, the formulashould appear-as shown below instead of as in the patentmmQwomommo01110511,

Signed and sealed this 20th day of January 1959.

[SEAL] Attest KARL H. AXLINE, ROBERT C. WATSON, Attesting Oficer.Gammissz'oner of Patents.

1. AS COMPOSITIONS OF MATTER THE COMPOUNDS HAVING THE FORMULA